U.S. patent number 5,155,005 [Application Number 07/675,825] was granted by the patent office on 1992-10-13 for method of producing polychromatic colored image.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Masayuki Iwasaki, Morimasa Sato, Fumiaki Shinozaki.
United States Patent |
5,155,005 |
Sato , et al. |
October 13, 1992 |
Method of producing polychromatic colored image
Abstract
A method of producing a polychromatic colored image with clear
fine patterns, comprising the steps of: (a) contacting a
light-sensitive colored resin layer, provided on a temporary
support transmissive of ultraviolet rays with an adhesive layer
provided on a permanent support; (b) imagewise exposing the
light-sensitive colored resin layer to a pattern through the
temporary support; (c) peeling the temporary support from the
imagewise exposed resin layer; (d) developing the imagewise exposed
colored resin layer to form a colored resin pattern on the adhesive
layer; (e) embedding the colored resin pattern into the surface of
the adhesive layer by applying pressure through a material having a
surface energy lower than that of both the colored resin pattern
and the adhesive layer; (f) contacting a light-sensitive resin
layer of another image-forming material colored in a tint different
from resin layers previously formed on the adhesive layer with the
adhesive layer; and (g) repeating the exposure, development and
embedding steps as described above; and (h) repeating these
processes until the desired number of colored patterns are formed
and embedded in the adhesive layer.
Inventors: |
Sato; Morimasa (Shizuoka,
JP), Iwasaki; Masayuki (Shizuoka, JP),
Shinozaki; Fumiaki (Shizuoka, JP) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Kanagawa, JP)
|
Family
ID: |
26423284 |
Appl.
No.: |
07/675,825 |
Filed: |
March 27, 1991 |
Foreign Application Priority Data
|
|
|
|
|
Mar 29, 1990 [JP] |
|
|
2-82262 |
Sep 3, 1990 [JP] |
|
|
2-232854 |
|
Current U.S.
Class: |
430/257; 430/258;
430/7 |
Current CPC
Class: |
G02F
1/133516 (20130101); G03F 3/10 (20130101); G03F
7/0007 (20130101); G03F 7/0035 (20130101); G03F
7/40 (20130101) |
Current International
Class: |
G02F
1/13 (20060101); G02F 1/1335 (20060101); G03F
7/40 (20060101); G03F 3/10 (20060101); G03F
7/00 (20060101); G03C 011/12 (); G03F 007/26 () |
Field of
Search: |
;430/257,258,7 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Schilling; Richard L.
Attorney, Agent or Firm: Sughrue, Mion, Zinn, Macpeak &
Seas
Claims
What is claimed is:
1. A method of producing a polychromatic colored image having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising said light-sensitive resin layer
provided on a temporary support transmissive of ultraviolet rays
with an adhesive layer provided on a permanent support;
(b) imagewise exposing the light-sensitive resin layer to a pattern
through the temporary support;
(c) peeling the temporary support from the imagewise exposed
light-sensitive resin layer;
(d) developing the imagewise exposed light-sensitive resin layer to
form a colored pattern on the adhesive layer;
(e) embedding the colored pattern formed on the adhesive layer into
the surface of the adhesive layer by applying pressure to the
colored pattern through a material having a surface energy lower
than that of both of the patterned resin layer and adhesive
layer;
(f) contacting a light-sensitive resin layer of another
image-forming material comprising a light-sensitive resin layer
provided on a temporary support transmissive of ultraviolet rays
and which resin layer is colored in a tint different from resin
layers previously formed on the adhesive layer with the
pattern-embedded adhesive layer;
(g) repeating steps (b) to (e); and
(h) repeating step (f) followed by steps (b) to (e) n-2 times to
form and embed n colored patterns into the adhesive layer.
2. A method of producing a polychromatic colored image having on
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising a light-sensitive resin layer
provided on a temporary support transmissive of ultraviolet rays
with an adhesive layer provided on a permanent support;
(b) imagewise exposing the light-sensitive resin layer to a pattern
through the temporary support;
(c) peeling the temporary support from the imagewise exposed
light-sensitive resin layer;
(d) developing the imagewise exposed light-sensitive resin layer to
form a colored pattern on the adhesive layer;
(e) contacting a light-sensitive resin layer of another
image-forming material having the same structure as that of step
(a), except for having a resin layer colored in a tint different
from resin layers previously formed on the adhesive layer with the
adhesive layer on which a colored pattern is formed;
(f) imagewise exposing the light-sensitive resin layer to a pattern
through the temporary support;
(g) peeling the temporary support from the imagewise exposed
light-sensitive resin layer;
(h) developing the light-sensitive resin layer in a developer to
form a colored pattern on the adhesive layer;
(i) repeating steps (e) to (h) n-2 times to form n colored patterns
on the adhesive layer; and
(j) embedding the colored patterns colored in at least two
different tints which have been formed on the adhesive layer into
the surface of the adhesive layer by applying pressure thereto
through a material having a surface energy lower than the colored
resin patterns and the adhesive layer.
3. A method as in claim 1, wherein a peel-apart layer transmissive
of ultraviolet rays is arranged in between the light-sensitive
resin layer and the temporary support of each of image forming
materials.
4. A method of producing a polychromatic colored image having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising said light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, with an
adhesive layer provided on a permanent support;
(b) peeling the temporary support from the peel-apart layer;
(c) imagewise exposing the light-sensitive resin layer to a pattern
through the peel-apart layer;
(d) developing the light-sensitive resin layer in a developer to
simultaneously remove the peel-apart layer through dissolution in
the developer and to form a colored pattern on the adhesive
layer;
(e) embedding the colored pattern formed on the adhesive layer into
the surface of the adhesive layer by applying pressure to the
colored pattern through a material having a surface energy lower
than that of both the patterned resin layer and the adhesive
layer;
(f) contacting a light-sensitive resin layer of another
image-forming material comprising a light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, and which
resin layer is colored in a tint different from the resin layers
previously formed on the adhesive layer, with the pattern-embedded
adhesive layer;
(g) repeating steps (b) to (e); and
(h) repeating step (f) followed by steps (b) to (e) n-2 times to
form and embed n colored patterns into the adhesive layer.
5. A method of producing a polychromatic colored image having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising said light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, with an
adhesive layer provided on a permanent support;
(b) peeling the temporary support from the peel-apart layer;
(c) imagewise exposing the light-sensitive resin layer to a pattern
through the peel-apart layer;
(d) developing the light-sensitive resin layer in a developer to
simultaneously remove the peel-apart layer through dissolution and
to form a first colored pattern on the adhesive layer;
(e) contacting a light-sensitive resin layer of another
image-forming material comprising a light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, and which
resin layer is colored in a tint different from the resin layers
previously formed on the adhesive layer, with the adhesive layer on
which a colored pattern is formed;
(f) imagewise exposing of the light-sensitive resin layer to a
pattern through the temporary support;
(g) peeling the temporary support from the peel-apart layer;
(h) developing the light-sensitive resin layer in a developer to
from a colored pattern on the adhesive layer;
(i) repeating steps (e) to (h) n-2 times to form n colored patterns
on the adhesive layer; and
(j) embedding the colored patterns colored in at least two
different tints which have been formed on the adhesive layer into
the surface of the adhesive layer by applying pressure thereto
through a material having a surface energy lower than the colored
resin patterns and the adhesive layer.
6. A method of producing a polychromatic colored image having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising said light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, with an
adhesive layer provided on a permanent support;
(b) peeling the temporary support form the peel-apart layer;
(c) imagewise exposing the light-sensitive resin layer to a pattern
through the peel-apart layer;
(d) removing the peel-apart layer by washing with water;
(e) developing the light-sensitive resin layer in a developer to
form a colored pattern on the adhesive layer;
(f) embedding the colored pattern formed on the adhesive layer into
the surface of the adhesive layer by applying pressure to the
colored pattern through a material having a surface energy lower
than that of both of the colored resin pattern and the adhesive
layer;
(g) contacting light-sensitive resin layer of another image-forming
material comprising a light-sensitive resin layer provided on a
temporary support via a peel-apart layer, which peel-apart layer is
transmissive to ultraviolet rays, and which resin layer is colored
in a tint different from the resin layers previously formed on the
adhesive layer, with the pattern-embedded adhesive layer;
(h) repeating steps (b) to (f); and
(i) repeating step (g) followed by steps (b) to (f) n-2 times to
form and embed n colored patterns into the adhesive layer.
7. A method of producing a polychromatic colored image having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising said light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, with an
adhesive layer provided on a permanent support;
(b) peeling the temporary support from the peel-apart layer;
(c) imagewise exposing the light-sensitive resin layer to a pattern
through the peel-apart layer;
(d) removing the peel-apart layer by washing with water;
(e) developing the light-sensitive resin layer in a developer to
form a colored pattern on the adhesive layer;
(f) contacting a light-sensitive resin layer of another
image-forming material comprising a light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, and which
resin layer is colored in a tint different from the resin layers
previously formed on the adhesive layer, with the adhesive layer on
which a colored pattern is formed;
(g) peeling the temporary support from the peel-apart layer;
(h) imagewise exposing the light-sensitive resin layer to a pattern
through the peel-apart layer;
(i) removing the peel-apart layer by washing with water;
(j) developing the light-sensitive resin layer in a developer to
form a colored pattern on the adhesive layer;
(k) repeating steps (f) to (j) n-2 times to form n colored patterns
on the adhesive layer; and
(1) embedding the colored patterns colored in at least two
different tints which have been formed on the adhesive layer into
the surface of the adhesive layer by applying pressure thereto
through a material having a surface energy lower than that of the
colored resin patterns and the adhesive layer.
8. A method as in claim 1, wherein the colored images embedded in
the adhesive layer include red, green, blue and black patterns, and
the permanent support is substantially transparent.
9. A method as in claim 1, wherein said colored images embedded in
the adhesive layer include yellow, cyan, magenta and black
patterns.
10. A method as in claim 1, wherein the adhesive layer comprises a
negatively working light-sensitive resin composition having a
softening point of from 10.degree. C. to 140.degree. C and which
resin composition is resistant to an alkali developing
solution.
11. A method as in claim 10, wherein the adhesive layer of the
negatively working light-sensitive resin composition has a
photosensitivity lower than about one-third the photosensitivity of
each of the colored light-sensitive resin layers.
12. A method as in claim 11, further comprising the step of
exposing the adhesive layer having the embedded colored patterns to
light to cure the adhesive layer.
13. A method as in claim 10, wherein the adhesive layer of the
negatively working light-sensitive resin composition has a
photosensitivity at wavelength ranges substantially different from
those wavelength ranges at which the light-sensitive colored resin
layers are photosensitive.
14. A method as in claim 2, wherein a peel-apart layer transmissive
to ultraviolet rays is arranged between the light-sensitive resin
layer and the temporary support of each of the image forming
materials.
15. A method as in claim 4, wherein the peel-apart layer has a
thickness of from 0.2 to 10.0 .mu.m.
16. A method as in claim 1, wherein each of the light-sensitive
resin layers has a dry thickness of from 0.3 to 10 .mu.m.
17. A method as in claim 1, wherein the permanent support is
selected from a biaxially stretched polyethylene terephthalate film
and a glass plate.
18. A method as in claim 1, wherein each of the adhesive layers has
a thickness of from 1 to 100 .mu.m.
19. A method as in claim 1, wherein the material having a surface
energy lower than that of both of the patterned resin layer and the
adhesive layer is selected from a silicone resin and a
fluorine-containing resin in the form of a film having a thickness
of from 5 to 200 .mu.m.
20. A method as in claim 1, wherein a pressure of from 1.5 to 2.5
kg/cm.sup.2 is applied to embed the colored pattern into the
surface of the adhesive layer.
Description
FIELD OF THE INVENTION
The present invention relates to a method of producing
poly-chromatic colored images on substrates for color filters for
use in a liquid crystal color display and the like, and for other
color display plates.
BACKGROUND OF THE INVENTION
Generally, the structure of a liquid crystal color display
comprises a first multilayer construction having provided on a
transparent substrate such as a glass plate and laminated in the
following order, a color filter, a protective film, a clear
electrode having a matrix-form pattern, an insulating film and an
orientation film, and a second multilayer construction provided on
a transparent substrate such as a glass plate and laminated in the
following order, a sheet-form or striped-pattern of clear electrode
and an orientation film, said multilayer structures being opposed
such that their respective orientation films face each other to
form an inner cell having a thickness defined by a spacer, which
cell contains a liquid crystal material. The composite structure is
arranged between two polarizing plates. Alternatively, in the first
multilayer construction, the clear electrode having a matrix-form
pattern may be positioned between the color filter and the
transparent substrate.
The color filter generally comprises red, blue and green dot-form
images each arranged in a matrix pattern, and their respective
boundaries are partitioned by a black matrix.
Also, automobile meters and tachometer panels a generally employ a
plastic substrate provided with images of various colors including
yellow, cyan, magenta and black colors.
For the purpose of forming colored images on a support as in the
above noted applications, a wide variety of methods have hitherto
been proposed.
For example, the preparation of a color filter for a liquid crystal
display is discussed below.
First, a multicolor image is formed on a transparent substrate,
such as a glass plate, used as a support in accordance with (1) a
dyeing method, (2) a printing method, or (3) a method using
light-sensitive colored resin solutions (i.e., a colored resist
method) as disclosed in JP-A-63-298304 (The term "JP-A" as used
herein means an "unexamined published Japanese patent
application"), JP-A-63-309916, JP-A-01-152449, etc., wherein a
light-sensitive colored resin solution is coated, exposed and
developed in succession, and these steps are then repeated. Also, a
multicolor image can be formed using (4) a method which comprises
transferring successively colored images formed on their respective
temporary supports onto a final support or another temporary
support, as disclosed in JP-A-61-99103, JP-A-61-233704 or JP-
A-61-279802, (5) a method as disclosed in JP-A-61-99102, wherein a
previously colored light-sensitive resin solution is coated on a
temporary support to form a colored layer, the colored layer is
transferred directly onto a transparent substrate and then
subjected successively to exposure and development, and these steps
are then repeated, or (6) a method as disclosed in JP-A-61-256303,
which comprises forming a multicolor image on a temporary support
by repetition of steps consisting of transfer of a light-sensitive
colored layer onto a temporary support, exposure and development,
and transferring the thus formed multicolor image onto a final
support such as a glass plate. In addition, an electrodeposition
method, a photographic method, an evaporation method, a
decolorization method, etc., have been used for the above-described
purpose.
A protective layer is then formed on the polychromatic colored
image for the purpose of physically and chemically protecting the
colored image and for leveling the image surface. The protective
layer generally comprises a film of high transparency, e.g., a
resin film of acryl, urethane, silicone or like type, or a film of
metal oxide such as silicon oxide, that is formed using a spin
coating process, a roll coating process, a printing process, etc.
If necessary, the structure is subjected to level standing and
solvent removal, followed by a cure processing.
On the protective layer, a transparent conductive film, such as a
tin indium oxide (ITO) film or a tin oxide film, is further formed
using a vacuum film-forming process, such as a sputtering process,
a vacuum deposition process or the like. An electrode pattern is
then formed using a mask evaporation method, an etching method
etc., to form a clear patterned electrode layer. The clear
patterned layer may also be formed on the transparent substrate
below the colored image and the black matrix layer.
Each of the above described conventional methods for forming
colored images in the preparation of a color filter are
disadvantageous for various reasons as discussed below.
In the dyeing method (1), the steps of coating a photoresist and
partly dyeing the dried transparent film are repeated. Thus,
repetition of the formation and removal of a reserve printing layer
is required such that the production process is complex.
In the printing method (2), the printing ink is poorly transferable
to glass such that the colored patterns tend to be inferior in
shape and uneven in density. Also, registering is required to
prepare three or four differently colored patterns. Therefore, it
is difficult to form a color filter of high quality using this
method.
In the method (3), the density of the colored layer varies with the
thickness of the layer, such that an accurate coating technique is
required to provide uniform density throughout the colored layer.
In addition, the second colored layer is difficult to coat
uniformly since the first colored layer formed prior to coating of
the second colored layer has an uneven surface.
In the method (4), it is difficult to precisely arrange images of
different colors at their individually intended positions
(hereinafter, "registering") upon multiple separate transfers of
the colored images to the final support.
As for the methods (5) and (6), although the process for forming
colored images is simplified, and although it is easy to control
exposure, development and density, and although the registering is
also performed without difficulty, these methods are still
disadvantageous for reasons as follows.
JP-A-61-99102, JP-A-61-256303 and JP-A-63-187203 disclose methods
of producing a color filter, which comprise providing
light-sensitive colored resin layers on the surface of a
transparent substrate using a transfer technique, and transferring
to the final support which is substantially transparent.
Transferrable red, blue and green images are formed one after
another by imagewise exposure and development. According to these
methods, no deviation is caused in the transfer step with respect
to the registering of differently colored images. Therefore, these
methods are attractive. Moreover, since the light-sensitive colored
resin layers previously coated in a uniform and definite thickness
are transferred, exposure and development characteristics are
stabilized, and good density control of colored images is
realized.
However, the colored image that is first formed on the adhesive
layer has a height of several microns in accordance with these
methods, such that sufficient interlayer contact cannot be realized
upon the subsequent transfer of additional colored light-sensitive
resin layers. Consequently, colored images formed through exposure
and subsequent development steps after the formation of the first
colored image are not in sufficient contact with one another.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide a method of
producing polychromatic colored images on separate supports for the
production of color filters or the like, in high throughput.
A second object of the present invention is to provide a method of
producing a highly precise polychromatic colored image composed of
differently colored clear image patterns which exhibit distinct
boundaries between image patterns without blurring.
A third object of the present invention is to provide a method of
producing a polychromatic colored image having enhanced registering
accuracy for differently colored image patterns, and which method
facilitates the registering operation.
A fourth object of the present invention is to provide a method of
producing a polychromatic colored image at low cost using a
simplified process.
The above-described objects of the present invention are achieved
by each of the following methods:
1. A method of producing a polychromatic colored image, having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising said light-sensitive resin layer
provided on a temporary support transmissive of ultraviolet rays
with an adhesive layer provided on a permanent support;
(b) imagewise exposing the light-sensitive resin layer to a pattern
through the temporary support;
(c) peeling the temporary support from the imagewise exposed
light-sensitive resin layer;
(d) developing the imagewise exposed light-sensitive resin layer in
a developer to form a colored pattern on the adhesive layer;
(e) embedding the colored pattern formed on the adhesive layer into
the surface of the adhesive layer by applying pressure to the
colored pattern through a material having a surface energy lower
than that of both of the patterned resin layer and the adhesive
layer;
(f) contacting a light-sensitive resin layer of another
image-forming material comprising a light-sensitive resin layer
provided on a temporary support transmissive of ultraviolet rays
and which resin layer is colored in a tint different from resin
layers previously formed on the adhesive layer with the pattern
embedded adhesive layer;
(g) repeating steps (b) to (e); and
(h) repeating step (f) followed by steps (b) to (e) n-2 times to
form and embed n colored patterns into the adhesive layer.
2. A method of producing a polychromatic colored image having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising a light-sensitive resin layer
provided on a temporary support transmissive of ultraviolet rays
with an adhesive layer provided on a permanent support;
(b) imagewise exposing the light-sensitive resin layer to a pattern
through the temporary support;
(c) peeling the temporary support from the imagewise exposed
light-sensitive resin layer;
(d) developing the imagewise exposed light-sensitive resin layer to
form a colored pattern on the adhesive layer;
(e) contacting a light-sensitive resin layer of another
image-forming material having the same structure as that of step
(a) except for having a resin layer colored in a tint different
from resin layers previously formed on the adhesive layer with the
adhesive layer on which a colored pattern is formed;
(f) imagewise exposing the light-sensitive resin layer to a pattern
through the temporary support,
(g) peeling the temporary support from the imagewise exposed
light-sensitive resin layer;
(h) developing the light-sensitive resin layer in a developer to
form a colored pattern on the adhesive layer;
(i) repeating steps (e) to (h) n-2 times to form n colored patterns
on the adhesive layer; and
(j) embedding the colored patterns colored in at least two
different tints which have been formed on the adhesive layer into
the surface of the adhesive layer by applying pressure thereto
through a material having a surface energy lower than the colored
resin patterns and the adhesive layer.
3. A method of producing a polychromatic colored image having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising said light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, with an
adhesive layer provided on a permanent support;
(b) peeling the temporary support from the peel-apart layer;
(c) imagewise exposing the light-sensitive resin layer to a pattern
through the peel-apart layer;
(d) developing the light-sensitive resin layer in a developer to
simultaneously remove the peel-apart layer through dissolution in
the developer, and to form a colored pattern on the adhesive
layer;
(e) embedding the colored pattern formed on the adhesive layer into
the surface of the adhesive layer by applying pressure to the
colored pattern through a material having a surface energy lower
than both the patterned resin layer and the adhesive layer;
(f) contacting a light-sensitive resin layer of another
image-forming material comprising a light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, and which
resin layer is colored in a tint different from the resin layers
previously formed on the adhesive layer with the pattern-embedded
adhesive layer;
(g) repeating step (b) to (e); and
(h) repeating step (f) followed by steps (b) to (e) n-2 times to
form and embed n colored patterns into the adhesive layer.
4. A method of producing a polychromatic colored image having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising said light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, with an
adhesive layer provided on a permanent support;
(b) peeling the temporary support from the peel-apart layer;
(c) imagewise exposing the light-sensitive resin layer to a pattern
through the peel-apart layer;
(d) developing the light-sensitive resin layer in a developer to
simultaneously remove the peel-apart layer through dissolution and
to form a colored pattern on the adhesive layer;
(e) contacting a light-sensitive resin layer of another
image-forming material comprising a light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, and which
resin layer is colored in a tint different from the resin layers
previously formed on the adhesive layer, with the adhesive layer on
which a colored pattern is formed;
(f) imagewise exposing the light-sensitive resin layer to a pattern
through the temporary support,
(g) peeling the temporary support from the peel-apart layer;
(h) developing the light-sensitive resin layer in a developer to
form a colored pattern on the adhesive layer;
(i) repeating steps (e) to (h) n-2 times to form n colored patterns
on the adhesive layer; and
(j) embedding the colored patterns colored in at least two
different tints which have been formed on the adhesive layer into
the surface of the adhesive layer by applying pressure thereto
through a material having a surface energy lower than the colored
resin patterns and the adhesive layer.
5. A method of producing a polychromatic colored image having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising said light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, with an
adhesive layer provided on a permanent support;
(b) peeling the temporary support from the peel-apart layer;
(c) imagewise exposing the light-sensitive resin layer to a pattern
through the peel-apart layer;
(d) removing the peel-apart layer by washing with water;
(e) developing the light-sensitive resin layer in a developer to
form a colored pattern on the adhesive layer;
(f) embedding the colored pattern formed on the adhesive layer into
the surface of the adhesive layer by applying pressure to the
colored pattern through a material having a surface energy lower
than both that of the colored resin pattern and the adhesive
layer;
(g) contacting a light-sensitive resin layer of another
image-forming material comprising a light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, and which
resin layer is colored in a tint different from the resin layers
previously formed on the adhesive layer, with the pattern-embedded
adhesive layer;
(h) repeating steps (b) to (f); and
(i) repeating steps (g) followed by steps (b) to (f) n-2 times to
form and embed n colored patterns into the adhesive layer.
6. A method of producing a polychromatic colored image having an
integer value of n colored patterns (n.gtoreq.2), comprising the
steps of:
(a) contacting a light-sensitive colored resin layer of an
image-forming material comprising said light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, with an
adhesive layer provided on a permanent support;
(b) peeling the temporary support from the peel-apart layer;
(c) imagewise exposing the light-sensitive resin layer to a pattern
through the peel-apart layer;
(d) removing the peel-apart layer by washing with water;
(e) developing the light-sensitive resin layer in a developer to
form a colored pattern on the adhesive layer;
(f) contacting a light-sensitive resin layer of an another
image-forming material comprising a light-sensitive resin layer
provided on a temporary support via a peel-apart layer, which
peel-apart layer is transmissive to ultraviolet rays, and which
resin layer is colored in a tint different from the resin layers
previously formed on the adhesive layer, with the adhesive layer on
which a colored pattern is formed;
(g) peeling the temporary support from the peel-apart
(h) imagewise exposing the light-sensitive resin layer to a pattern
through the peel-apart layer;
(i) removing the peel-apart layer by washing with water;
(j) developing the light-sensitive resin layer in a developer to
form a colored pattern on the adhesive layer;
(k) repeating steps (f) to (j) n-2 times to form n colored patterns
on the adhesive layer; and
(1) embedding the colored patterns colored in at least two
different tints which have been formed on the adhesive layer into
the surface of the adhesive layer by applying pressure thereto
through a material having a surface energy lower than that of the
colored resin patterns and the adhesive layer.
DETAILED DESCRIPTION OF THE INVENTION
The process of embedding a colored pattern in the surface of the
adhesive layer by the application of pressure, which embedding may
be carried out each time a pattern of a particular color has been
formed and has not yet been laminated with a light-sensitive resin
layer colored in a second tint, can also be performed at the
conclusion of all the individual processes for forming patterns of
different colors. Patterns of different colors are prepared by
forming a pattern of a particular color, immediately thereafter
laminating the formed pattern with a light-sensitive resin layer
colored in a second tint, exposing and developing the resin layer
to form a second pattern of the second color, and repeating these
image-forming processes to obtain the number of desired colored
patterns.
It is essential to the present invention that the processes
described and claimed herein are carried out in their order of
description. Other processes which have no adverse influence on the
effects of the present invention, for example, a washing process
subsequent to the development, may be safely inserted within the
processing sequence.
In accordance with the present invention, the following advantages
are realized.
(1) Exposure and development characteristics are stabilized, and
the control of color density is facilitated, because image-forming
materials previously colored in different tints, each of which has
a uniform coating thickness, are used;
(2) The registering of patterns with different colors is simply
conducted;
(3) The polychromatic colored image thereby obtained is excellent
in flatness, because the patterns are, in a substantial sense,
embedded in the adhesive layer, and the patterns, as the whole, are
excellent in adhesiveness to the support and in accuracy;
(4) The colored image thereby obtained have high durability;
(5) Coating problems, for example, stability of coating
compositions, are avoided, because the light-sensitive materials
are supplied in the form of a colored layer; and
(6) Adhesion of the produced image when using a glass support is
satisfactory, because an adhesive layer is provided on the support,
etc.
Materials for use in the present invention are described below in
detail.
The temporary support having provided thereon a light-sensitive
colored resin layer for use in the present invention should have
flexibility, is preferably transmissive to ultraviolet rays, and
which does not substantially deform, shrink or elongate under
applied pressure, or under applied pressure and heat. Useful
temporary supports include a polyethylene terephthalate film, a
cellulose triacetate film, a polystyrene film, a polycarbonate
film, etc. Among these films, biaxially stretched polyethylene
terephthalate films are preferred. The temporary support to be used
in the present invention generally has a thickness of from 10 to
200 .mu.m, preferably from 50 to 175 .mu.m, and more preferably
from 75 to 100 .mu.m.
On the temporary support, a light-sensitive colored resin layer is
provided directly or via a peel-apart layer arranged between the
resin layer and the temporary support, which peel-apart layer is
transmissive to ultraviolet rays.
When the light-sensitive colored resin layer is provided directly
onto the transparent support, the temporary support is transmissive
to ultraviolet rays to an extent sufficient to cure the resin
layer. On the other hand, when the resin layer is provided through
a peel-apart layer, ultraviolet transmission is not essential for
the temporary support because the exposure can be carried out after
the temporary support is peeled apart from the resin layer.
The peel-apart layer is provided in order to enable the temporary
support to be readily peeled apart from the colored light-sensitive
resin layer after the resin layer is adhered to the permanent
support. Although the peeling can be carried out either before or
after imagewise exposure, peeling before the exposure is preferred
for enhancing the resolving power of the images. In this case, it
is desirable that the peel-apart layer is reading peeled from the
temporary support and also has moderate adhesiveness to the
temporary support such that oxygen from the air, which inhibits the
photosetting reaction in the light-sensitive color resin layer upon
imagewise exposure, is not diffused into the resin layer. Also, the
peel-apart layer is designed so as not to be mechanically peeled
apart from the resin layer, and to prevent oxygen gas from the
ambient from reaching the resin layer.
Such a peel-apart layer as described above can be formed by coating
a polymer solution onto the temporary support. Examples of useful
polymers for forming the peeling-apart layer include polyvinyl
alcohol, water-soluble partially esterified, etherified or
acetalated polyvinyl alcohols, 88-99% hydrolyzed polyvinyl acetate,
gelatin, gum arabic, methyl vinyl ether/maleic anhydride
copolymers, polyvinyl pyrrolidone, high molecular weight
water-soluble ethylene oxide polymers having a mean molecular
weight of from 100,000 to 3,000,000 and mixtures of two or more of
these polymers, as described in JP-B-46-32714 and JP-B-56-40824
(The "JP-B" as used herein means an "examined Japanese patent
publication") (corresponding to U.S. Pat. No. 3,884,693).
In forming the peel-apart layer on the temporary support, a coating
solution containing a polymer as described above dissolved in water
or a mixture of water with an organic solvent is used. When a
surface active agent is further added to this solution, a more
uniform peel-apart layer is obtained. The peel-apart layer
preferably has a thickness of from 0.2 to 10.0 .mu.m, and more
preferably from 0.5 to 5.0 .mu.m. When the layer has a thickness of
less than 0.2 .mu.m, the peeling-apart layer does not effectively
protect the resin layer from oxygen, whereas when the thickness is
increased beyond 10 .mu.m, the time for dissolving the layer in a
developer is excessive.
Useful surface active agents for the peel-apart coating solution
include anionic, cationic and nonionic surface active agents with
specific examples thereof including sodium C.sub.12-18
alkylsulfates or alkylsulfonates (such as sodium dodecylsulfate,
sodium octadecylsulfonate, etc.), N-cetyl-betaine, C-cetylbetaine,
alkylaminocarboxylates, alkylaminodicarboxylates, and polyethylene
glycols having a mean molecular weight of less than 400.
The colored light-sensitive resin layer provided on the temporary
support or peeling-apart layer is formed by coating a negatively
working light-sensitive resin composition having dissolved or
dispersed therein a dye or pigment of the desired color.
Negatively working light-sensitive resin compositions for use in
the present invention include those broadly divided into, e.g.,
four main groups as described below.
(1) Light-sensitive resin compositions comprising a negatively
working light-sensitive diazo resin and a binder
Useful examples of this type of negatively working light-sensitive
diazo resin include those disclosed in U.S. Pat. Nos. 2,063,631 and
2,667,415, or the reaction products of diazonium salts with
reactive carbonyl group-containing organic condensing agents, such
as formaldehyde. In particular, the condensation product of
diazodiphenylamine-p-diazonium salt and formaldehyde is preferred.
In addition to these diazo resins, those disclosed in
JP-B-49-48001, JP-B-49-45322 and JP-B-49-45323 are also useful.
The above described negatively working light-sensitive diazo resins
are soluble in water, such that they can be used in the form of an
aqueous coating solution in forming a light-sensitive resin layer.
On the other hand, these water-soluble diazo resins can be
converted into a substantially water-insoluble but organic
solvent-soluble form by reacting with aromatic or aliphatic
compounds containing one or more of a phenolic hydroxyl group
and/or a sulfo group in accordance with the method described in
JP-B-47-1167. Suitable examples of compounds containing phenolic
hydroxyl group(s) include hydroxybenzo-phenones such as
4-hydroxybenzophenone, 2,4-dihydroxybenzo-phenone,
2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy
-4,4'-dimethoxybenzophenone and
2,2',4,4'-tetrahydroxybenzo-phenone;
4,4--bis(4'-hydroxyphenyl)pentanoic acid, resorcinol, and those
having alkyl, alkoxy and/or like substituent(s) on the benzene
rings of these compounds; etc. Suitable examples of sulfonic acids
include aromatic sulfonic acids, such as benzenesulfonic acid,
toluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic
acid, phenolsulfonic acid, naphtholsulfonic acid,
benzophenonesulfonic acid, etc.; and soluble salts of these
sulfonic acids, such as ammonium salts thereof, and alkali metal
salts thereof. These sulfo group-containing compounds may be
substituted by one or more of a lower alkyl group, a nitro group,
or a halogen atom. Specific examples of preferred sulfo
group-containing compounds include benzenesulfonic acid,
toluenesulfonic acid, naphthalenesulfonic acid,
2,5-dimethylbenzenesulfonic acid, sodium benzenesulfonate,
naphthalene-2-sulfonic acid, 1-naphthol-2-sulfonic acid,
1-naphthol-4-sulfonic acid, 2,4-dinitro-1-naphthol-7-sulfonic acid,
hydroxy-4-methoxybenzophenone -5-sulfonic acid,
o-toluidine-m-sulfonic acid, and ethanesulfonic acid.
As for the preparation of the above described substantially
water-insoluble light-sensitive diazo resins, an aqueous solution
of a water-soluble light-sensitive diazo resin and that of a phenol
compound or a sulfonic acid compound are mixed in about equimolar
amounts, based on the diazonium group and the phenolic or sulfo
group, respectively, to form the isolated product as a
precipitate.
In addition, the light-sensitive diazo resins disclosed in British
Patent 1,312,925 are also favored. A highly desirable
light-sensitive diazo resin is the
2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid salt of
p-diazodiphenylamine-formaldehyde condensate.
The light-sensitive diazo resin is contained in the light-sensitive
resin layer in an amount of from 5 to 50% by weight based on the
total weight of the light-sensitive resin layer. When the content
of the light-sensitive diazo resin is increased, the storage
stability is lowered although the sensitivity is enhanced. A
particularly preferred content of the light-sensitive diazo resin
in the light-sensitive resin layer is from 8 to 20% by weight.
The binder for use in the light-sensitive resin layer includes
various high molecular weight compounds. Preferred binders are
those containing carboxyl, hydroxyl, amino, carbonamido,
sulfonamido, active methylene, thioalcoholic and/or epoxy groups in
the molecule thereof.
For a water-soluble light-sensitive resin composition, the
combination of a water-soluble light-sensitive diazo resin with a
water-soluble binder is employed. Typical examples of the
water-soluble binder include polyvinyl alcohol, polyvinyl
pyrrolidone, polyacrylamide, hydroxymethyl cellulose, gelatin, etc.
On the other hand, binders suitable for the use in a
water-insoluble light-sensitive resin composition, which is
preferred with respect to storage stability, include the shellac as
disclosed in British Patent 1,350,521; polymers containing
hydroxyethyl(meth)acrylate as a constitutional repeating unit as
disclosed in British Patent 1,460,978 and U.S. Pat. No. 4,123,276;
the polyamide resin disclosed in U.S. Pat. No. 3,751,257; the
phenol resins disclosed in British Patent 1,074,392; polyvinyl
acetal resins such as polyvinyl formal resin, polyvinyl butyral,
etc.; the linear polyurethane resin disclosed in U.S. Pat. No.
3,660,097; polyvinyl alcohol phthalate resins; epoxy resins, or
polycondensates of bisphenol A and epichlorohydrin; amino
group-containing polymers, such as polyaminostyrene,
polyalkylamino(meth)-acrylate, etc.; cellulose derivatives, such as
cellulose acetate, cellulose alkyl ether, cellulose acetate
phthalate, etc.; and water soluble polyvinyl alcohol.
The content of the binder in the light-sensitive resin layer is
preferably from 50 to 95% by weight based on the total weight of
the light-sensitive resin layer. When the content of the binder is
decreased, the sensitivity is enhanced but the storage stability is
lowered. The content of the binder is more preferably within the
range of from 80 to 92% by weight.
(2) Photopolymerizing compositions
A photopolymerizing composition for use in the present invention
essentially contains an addition polymerizing unsaturated monomer,
a photopolymerization initiator, and a binder. An addition
polymerizing unsaturated monomer is a compound containing in a
molecule thereof at least one ethylenic unsaturated group capable
of undergoing addition polymerization, and having a boiling point
of 100.degree. C. or higher under atmospheric pressure. Specific
examples of the addition polymerizing unsaturated monomer include
monofunctional acrylates and methacrylates, e.g., polyethylene
glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate,
phenoxyethyl(meth)acrylate, etc.; and polyfunctional acrylates and
methacrylates, e.g., polyethylene glycol di(meth)acrylate,
polypropylene glycol di(meth)acrylate, trimethylolethane
triacrylate, trimethylolpropane diacrylate, neopentyl glycol
di(meth)acrylate, pentaerythritol tetra (meth)acrylate,
pentaerythritol tri(meth)acrylate, dipentaerythritol
hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate,
hexanediol di(meth)acrylate, trimethylolpropane
tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl)isocyanurate,
tri(acryloyloxyethyl) cyanurate, glycerine tri(meth)acrylate;
reaction products obtained by carrying out the addition of a
polyfunctional alcohol, such as trimethylolpropane, glycerine or
the like, to ethylene oxide or propylene oxide, and then having the
resulting adduct undergo (meth)acrylation; urethaneacrylates as
disclosed in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; and
polyester acrylates and epoxyacrylates which are the reaction
products of epoxy resins and (meth)acrylic acid as disclosed in
JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Among the above
described moreovers, trimethylolpropane tri(meth)acrylate,
pentaerythritol tetra(meth)acrylate, dipentanerythritol
hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate are
preferred.
The content of the addition polymerizing unsaturated monomer in the
photopolymerizing composition is from 5 to 50% by weight,
preferably from 10 to 40% by weight, based on the total weight of
the photopolymerizing composition. When the content is lower than
5% by weight, the photosensitivity and the image strength are
reduced, whereas when the content of the addition polymerizing
unsaturated monomer is increased beyond 50% by weight, the
light-sensitive resin layer becomes too sticky.
Useful examples of the photopolymerization initiator, include
vicinal polyketaldonil as disclosed in U.S. Pat. No. 2,367,660, the
acyloin ether compounds as disclosed in U.S. Pat. No. 2,448,828,
the .alpha.-hydrocarbon substituted aromatic acyloin compounds as
disclosed in U.S. Pat. No. 2,722,512, polynuclear quinone compounds
as disclosed in U.S. Pat. Nos. 3,046,127 and 2,951,758, the
combinations of triarylimidazole dimers with p-aminoketones as
disclosed in U.S. Pat. No. 3,549,367, the benzothiazole compounds
and trihalomethyl -s-triazine compounds as disclosed in
JP-B-51-48516, the trihalomethyl-s-triazine compounds as disclosed
in U.S. Pat. No. 4,239,850, and the trihalomethyloxadiazole
compounds as disclosed in U.S. Pat. No. 4,212,976. Particularly
preferred among the above-noted photopolymerization initiators are
trihalomethyl-s-triazines, trihalomethyloxadiazoles, and
triarylimidazole dimers.
The content of the photopolymerization initiator in the
photopolymerizing composition is from 0.5 to 20% by weight,
preferably from 2 to 15% by weight, based on the total weight of
the photopolymerizing composition. When the content is less than
0.5% by weight, the photosensitivity and the image strength are
reduced, whereas when the content of the photopolymerization
initiator is more than 20% by weight further increase in effect is
not obtained.
A desirable binder is an organic linear macromolecule that is
compatible with addition polymerizing unsaturated monomers, soluble
in organic solvents, and soluble or at least sellable in a weak
alkaline aqueous solution. Useful examples of the organic linear
macromolecule as described above include polymers containing
carboxyl groups in their side chains, such as methacrylic acid
copolymers, acrylic acid copolymers, itaconic acid copolymers,
crotonic acid copolymers, maleic acid copolymers and partially
esterified maleic acid copolymers as disclosed in JP-A-59-44615,
JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836 and
JP-A-59-71048; and cellulose derivatives containing carboxyl groups
in the side chains thereof. In addition, those obtained by the
addition of cyclic acid anhydrides to hydroxyl group-containing
polymers are also useful. In particular, copolymers of
benzyl(metha)acrylate and (meth)acrylic acid, and plural copolymers
of benzyl(meth) acrylate, (meth)acrylic acid and other monomers are
preferred. Although all the above-noted binders are insoluble in
water, water-soluble polymers such as polyvinyl pyrrolidone,
polyethylene oxide, polyvinyl alcohol and the like, can be also
used as the binder.
Furthermore, alkali-insoluble polymers can be added for the purpose
of improving various properties, e.g., the strength of a cured
film, as long as the alkali-insoluble polymers do not exert any
adverse effects upon developability, etc. Examples of such polymers
include alcohol-soluble nylon and epoxy resins.
The content of the binder in the photopolymerizing composition is
from 50 to 95% by weight, preferably from 60 to 90% by weight,
based on the total weight of the photopolymerizing composition.
When the content is less than 50% by weight, the light-sensitive
resin layer is too tacky, whereas when the content of the binder is
increased beyond 95% by weight, the composition is reduced in
strength of the image formed and photosensitivity.
In addition to the above-described constituent elements, it is
desirable to further add a thermal polymerization inhibitor to the
photopolymerizing composition. Examples thereof include
hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol,
t-butylcatechol, benzoquinone,
4,4'-thiobis(3-methyl-6-t-butylphenol),
2,2'-methylenebis(4-methyl-6-t-butylphenol),
2-mercaptobenzimidazole, phenothiazine, etc.
(3) Light-sensitive resin compositions comprising an azide compound
and a binder
Suitable examples of the above-noted light-sensitive resin
composition include those which comprise an azide compound and a
high molecular weight binder soluble in water or an alkaline
aqueous solution as disclosed in British Patents 1,235,281 and
1,495,861, JP-A-51-32331, JP-A-51-36128, etc.; and those which
comprise an azido group-containing polymer and a high molecular
weight compound as a binder as disclosed in JP-A-50-5102,
JP-A-50-84302, JP-A-53-12984, etc.
These light-sensitive resin compositions are used in an amount so
as to give the colored pattern in the similar thickness as obtained
in the other light-sensitive resin compositions as mentioned
above.
(4) Cinnamic acid type light-sensitive resins
Suitable examples of the above note dresins include light-sensitive
polyesters as disclosed, e.g., in JP-A-52-96696, and polyvinyl
cinnamates as disclosed in British Patents 1,112,277, 1, 313,390,
1,341,004 and 1,377,747.
These light-sensitive resins are used in an amount so as to give
the colored pattern in the similar thickness as obtained in the
other light-sensitive-resin compositions as mentioned above.
In forming a colored light-sensitive resin layer comprising a
pigment or a dye and a negatively working light-sensitive resin
composition, the negatively working light-sensitive resin
composition is dissolved in a proper solvent, and therein is
dispersed a single pigment or a mixture of two or more pigments, or
dissolved a dye to prepare a coating composition colored in a
single hue. The coating composition is coated on a temporary
support as described above using a spinner, a whirler, a roller
coater, a curtain coater, a knife coater, a wire-bar coater, an
extruder, etc.
For color filters, red, green, blue and black pigments are used.
Preferred examples of these pigments include Carmine 6B (C.I.
12490), Phthalocyanine Green (C.I. 74260), Phthalocyanine Blue
(C.I. 74160), and Mitsubishi Carbon Black MA-100.
For display plates such as a meter panel for automobiles, yellow,
magenta, cyan and black pigments or dyes are used. In addition,
metal powders, white pigments, fluorescent pigments, etc. can also
be employed. Specific (examples of preferred pigments include #1201
Lionol Yellow (C.I. 21090), Lionol Yellow GRO (C.I. 21090), Shimura
Fast Yellow 8GF (C.I. 21105), Benzidine Yellow 4T-564D (C.I.
21095), Shimura Fast Red 4015 (C.I. 12355), Lionol Red 7B4401 (C.I.
15850), Fastgen Blue TGR-L (C.I. 74160), Lionol Blue SM (C.I.
26150), Mitsubishi Carbon Black MA-100, and Mitsubishi Carbon Black
#40. Preferred dyes include Victoria Pure Blue (C.I. 42595),
Auramine O (C.I. 41000), Carotene Brilliant Flavin (C.I. basic 13),
Rhodamine 6GCP (C.I. 45160), Rhodamine B (C.I. 45170), Safranine
OK70:100 (C.I. 50240), Erioglaucine X (C.I. 42080), and Fast Black
HB (C.I. 26150).
It is desirable that the pigment or dye as noted above is
incorporated in a light-sensitive resin layer to be colored in an
amount of from 1 to 30% by weight, preferably from 5 to 20% by
weight, based on the total weight of the light-sensitive resin
layer.
Solvents suitable for preparing the coating composition include
benzene, toluene, xylene, cyclohexane, ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether, propylene glycol monomethyl
ether, propylene glycol monoethyl ether, ethylene glycol monomethyl
ether acetate, ethylene glycol monoethyl ether acetate, propylene
glycol monomethyl ether acetate, propylene glycol monoethyl ether
acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone,
cyclohexa-none, methyl acetate, ethyl acetate, propyl acetate,
butyl acetate, methyl lactate, ethyl lactate, methanol, ethanol,
1-propanol, 2-propanol, butanol, secbutanol, tert-butanol,
N-methylpyrrolidone, dimethylformamide, dimethylacetamide,
.gamma.-butyrolactone, .epsilon.-caprolactame, dimethyl sulfoxide,
hexamethyl phosphoryl amide, and water. These solvents can be used
alone or in a mixture of two or more.
The concentration of solid components in the coating composition
ranges from 1 to 50% by weight, preferably from 5 to 40% by weight.
A dry thickness of the colored light-sensitive resin layer is
preferably from 0.3 to 10 .mu.m, more preferably from 0.5 to 5
.mu.m.
The permanent support provided with an adhesive layer is
substantially not deformed, shrunk or elongated under applied
pressure or under applied pressure and heat, and optionally is
transmissive to ultraviolet rays. Examples of such a support
include a polyethylene terephthalate film, a cellulose triacetate
film, a polystyrene film, a polycarbonate film, and a glass plate.
Among these materials, a biaxially stretched polyethylene
terephthalate film and a glass plate are preferred in
particular.
The permanent support which is preferably used in the present
invention include those having a thickness of from 0.1 to 10 mm,
preferably from 0.5 to 5 mm, and more preferably from 0.5 to 2
mm.
When the final colored images are utilized as color filters, it is
necessary for the support to be substantially transparent, and for
such a purpose, the above-cited polymer films or a glass plate can
be used as the support. Also, a transparent support provided with
matrix-form clear electrodes may be used.
When the final colored images are utilized as a color display
plate, transparent, translucent or opaque plastic films or plates,
glass plates and the like are suitably used as the support.
Specifically, polycarbonate plates, which may contain an opaque
inorganic filler are preferred.
On a permanent support as described above, an adhesive layer is
provided. The adhesive layer is such that it acquires satisfactory
adhesiveness to the above-described light-sensitive colored resin
layer when brought into contact with one another and to also ensure
sufficient adhesion when colored images formed by subjecting the
light-sensitive colored resin layer to imagewise exposure and
subsequent development are embedded therein. Furthermore, the
adhesive layer has sufficient resistance to an alkaline aqueous
developer used to develop the light-sensitive colored resin layer.
As the resistance to the alkaline, the adhesive layer is required
to withstand soaking in a 1% aqueous solution of sodium carbonate
at 33.degree. C. for 10 minutes.
In order to satisfy these requirements, the adhesive layer must be
soft at room temperature, or must become soft when heated. As such
an adhesive layer, those having a glass transition point of not
more than 130.degree. C., preferably not more than 100.degree. C.
and more preferably not more than 80.degree. C. are preferred.
Adhesive layers which satisfy the above requirements include a
layer formed by a thermoplastic polymer. Examples of such a
thermoplastic polymer include the image-accepting materials
disclosed in JP-A-51-5101.
Among such thermoplastic polymers, those having a glass transition
point within the range of 10.degree. C. to 140.degree. C. are
preferred.
As another example, layers containing pressure-sensitive adhesives
or heat-sensitive adhesives as disclosed in JP-B-46-15326 and
JP-B-59-14736 can be used in the present invention.
Adhesive layers preferably used in the present invention include
the photopolymerizable image-accepting layer as disclosed in
JP-A-59-97140, or the image-receiving layers disclosed in
JP-A-61-189535 and JP-A-01-65064 which have a two-layer structure
including a mold releasing layer. These layers are employed as an
adhesive layer, and irradiated with ultraviolet rays after the
images are embedded in the adhesive layer, resulting in the curing
of the adhesive layer. Thus, the adhesive layer is firmly adhered
to the support by this processing.
In this case, certain precautions must be taken in the pattern
exposure of the colored image-forming layer to avoid curing of the
photopolymerizable image-accepting layer. For example, the
photosensitivity of the photopolymerizable image-accepting layer is
adjusted to be less than about one-third that of the colored
image-forming layer, or photopolymerization initiators which are
photosensitive in different wave-length regions are employed.
The adhesive layer has a thickness sufficient to embed the colored
images therein after image formation. More specifically, a
thickness ranging from 1 to 100 .mu.m, especially from 5 to 30
.mu.m, is preferable. When the thickness is less than 1 .mu.m, the
embedding of the colored images therein is insufficient, and the
second colored image, etc. are inferior in closeness of contact
between the second and the successive colored images and the
adhesive layer, whereas when the adhesive layer is thicker than 100
.mu.m, the sheet provided therewith tends to exhibit a storage
problem.
The developer can be used as a bath, or in an atomized condition.
The removal of unexposed parts from the colored light-sensitive
resin layer can be carried out to advantage using known methods,
e.g., by rubbing with a brush, wet sponge and the like rubbing
means.
A medium used in developing the colored light-sensitive resin layer
after exposure is an aqueous medium, or a medium mainly containing
water. Also, it is preferable that an organic solvent compatible
with water and an alkaline substance are added to the developer, if
necessary.
Suitable examples of an organic solvent for addition to the
developer include methanol, ethanol, 2-propanol, 1-propanol,
butanol, diacetone alcohol, ethylene glycol monomethyl ether,
ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl
ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone,
.epsilon.-caprolactone, .gamma.-butyrolactone, dimethylformamide,
dimethylacetamide, and hexamethylphosphorylamide.
Suitable examples of an alkaline substance include hydroxides of
alkali metals [such as sodium hydroxide and potassium hydroxide),
carbonates of alkali metals (such as sodium carbonate and potassium
carbonate), hydrogen bicarbonates of alkali metals (such as sodium
hydrogen carbonate and potassium hydrogen carbonate), silicates of
alkali metals (such as sodium silicate and potassium silicate),
metasilicates of alkali metals (such as sodium metasilicate and
potassium metasilicate), triethanolamine, diethanolamine,
monoethanolamine, morpholine, trialkylammonium hydroxides, and
trisodium phosphate.
The developer may also contain a swelling agent.
Alkylnaphthalenesulfonates poor in foaming ability are preferred as
the swelling agent.
Particularly preferred developers, include an aqueous solution
containing ethylene glycol mono-n-butyl ether and sodium carbonate,
and an aqueous solution containing benzyl alcohol, sodium
carbonate, sodium hydroxide and sodium
butylnaphthalenesulfonate.
Materials having a lower surface energy than both the adhesive
layer and the colored images of the present invention include those
disclosed, for example, in JP-A-2-232854. Specific examples thereof
include silicone resins and fluorine-containing resins. In
embedding the colored image(s) formed on an adhesive layer into the
adhesive layer, pressure is applied thereto through a low
surface-energy material as described above. The pressure
application can be performed to advantage by using a roller made
from a low surface-energy material, or by inserting a film made
from a low surface-energy material or a flexible synthetic polymer
film coated with a low surface-energy material between the colored
image(s) on the adhesive layer and a roller made from rubber. A
suitable thickness for the film made from a low surface-energy
material is from 5 to 200 .mu.m, particularly preferably from 7 to
100 .mu.m. Preferable conditions for the embedding processing are a
pressure of from 1 to 3 Kg/cm.sup.2 and a processing speed of from
0.1 to 3 m/min, and more preferred conditions are a pressure of
from 1.5 to 2.5 Kg/cm.sup.2 and a processing speed of from 0.2 to 2
m/min.
In accordance with the present invention, it is preferred that heat
be applied simultaneously with the application of pressure. The
heat application is readily achieved using a roller equipped with a
heat evolving device on the inside thereof, and a surface
temperature of the roller is controlled to from 50.degree. to
160.degree. C., preferably from 80.degree. to 120.degree. C.
The present invention is illustrated in further detail below by
reference to the following examples. However, the invention is not
to be construed as being limited to these examples.
EXAMPLE 1
(An example of utilizing light-sensitive layers not having a
subbing layer and a monolayer-form photosensitive adhesive
layer)
Coating compositions for forming colored light-sensitive resin
layers were prepared comprising light-sensitive solutions of four
different colors including a black color (for a light-shielding
layer), a red color (for a R layer), a green color (for a G layer)
and a blue color (for a B layer) having the compositions shown in
the following Table 1 below.
TABLE 1 ______________________________________ (Coating
Compositions for Colored, Light-Sensitive Layers) Red Blue Green
Black (g) (g) (g) (g) ______________________________________
Benzylmethacrylate/Meth- 60 60 60 60 acrylic Acid Copolymer (molar
ratio = 73/27, viscosity = 0.12) Pentaerythritol Tetraacrylate 43.2
43.2 43.2 43.2 Michler's Ketone 2.4 2.4 2.4 2.4
2-(o-Chlorophenyl)-4,5-diphen- 2.5 2.5 2.5 2.5 ylimidazole Dimer
2.5 2.5 2.5 2.5 Irgadine Red BPT (red color) 5.4 Sudan Blue (blue
color) 5.2 Lead Phthalocyanine (green 5.6 color) Carbon Black
(black color) 5.6 Methyl Cellosolve Acetate 560 560 560 560 Methyl
Ethyl Ketone 280 280 280 280
______________________________________
These light-sensitive solutions were coated uniformly on four
separate polyethylene terephthalate films (20 .mu.m in thickness)
employed as temporary supports, and dried to form light-sensitive
colored resin layers each having a dry thickness of 0.5 .mu.m.
A 30 .mu.m-thick polyethylene film was laminated as a protective
film on each of the light-sensitive colored resin layers.
Thus, four kinds of light-sensitive colored resin sheets
(negatively working, light-sensitive, colored sheets) were
prepared, each consisting of the temporary support, the
light-sensitive colored resin layer and the protective film,
arranged in that order.
Separately, an adhesive layer was formed on a glass plate in the
following manner.
A 1.6 mm-thick glass plate was washed with a weak alkaline aqueous
solution, and then with water. After drying, the glass plate was
coated with the following coating composition for forming an
adhesive layer, and then dried. Thus, an adhesive layer having a
dry thickness of 5 .mu.m was formed. On this adhesive layer, a 30
.mu.m-thick polyethylene film was laminated as a protective
film.
______________________________________ Coating Composition for
Adhesive Layer: ______________________________________ Methyl ethyl
ketone 2,600 g Dianal BR-77 (acrylic resin, products 168 g of
Mitsubishi Rayon Company Limited) Dianal BR-64 (acrylic resin,
products 168 g of Mitsubishi Rayon Company Limited) Oxylac SH-101
(styrenemonopropyl 59 g maleate copolymer, products of Nippon
Shokubai Kagaku Kogyo Co., Ltd.) NK Ester TMMT (pentaerythritol
tetra- 216 g acrylate, products of Shin Nakamura Kagaku K.K.)
Megafac F-177P (fluorine-contained sur- 3.8 g face active agent,
products of Dai-Nippon Ink & Chemicals, Inc.) Hydroquinone
monomethyl ether 0.5 g Irgacure 651 (dimethoxyphenylacetophenone,
15 g products of Ciba Geigy Ltd.) Silane coupling agent KBM-403
(.gamma.-glycidoxy- 2.5 g propyltrimethoxysilane, products of
Shinetsu Silicone Co., Ltd.)
______________________________________
The protective film was peeled apart from the light-sensitive red
resin sheet. The resulting sheet was superposed on the glass plate
from which the protective film had been removed, such that the
light-sensitive resin layer was contacted with the adhesive layer
on the glass plate. Then, the superposed matter was subjected to a
laminating operation using a laminator (Fast Laminator 8B-550-80,
made by Taisei Shoji K.K.) under an applied pressure of 2
Kg/m.sup.2, a roller temperature of 105.degree. C., and a
laminating speed of 0.9 m/min. Thereafter, the temporary support
was peeled apart from the light-sensitive red resin sheet, whereby
the light-sensitive red resin layer was transferred to the glass
plate through the adhesive layer.
Subsequently, a photomask having a matrix-form pattern of elements
having a one-side length of 120 .mu.m was superposed upon the
light-sensitive red resin layer laminated on the adhesive layer,
and exposed by means of a ultra-high pressure mercury lamp of 2 Kw
provided with a cut-off filter for wavelengths below 400 nm, and
placed at a distance of 50 cm on the photomask side. The thus
exposed light-sensitive red resin layer was developed for 20
seconds at 35.degree. C. using a developer having the composition
described below, and subsequently washed with water and dried to
obtain a red image on the glass plate.
______________________________________ Composition of Developer:
______________________________________ Sodium carbonate 15 g Butyl
cellosolve 1 g Water 1 g ______________________________________
A 20 .mu.m-thick polyethylene terephthalate film, the surface of
which had been treated with a silicone lubricant, was inserted
between one of a pair of rollers and the red image on the adhesive
layer with its lubricant-treated face turned to the red image face,
and the red image covered with this film was passed between the
pair of rollers at a roller surface temperature of 105.degree. C.,
a between-roller pressure of 2.0 Kg/cm.sup.2 and a passing speed of
0.5 m/min, to thereby embed the red image into the adhesive
layer.
To the resulting adhesive layer was transferred the light-sensitive
resin layer of a green color in the same manner as described above.
Then, a matrix-form photomask was superposed on the light-sensitive
green resin layer in such a manner that the green image to be
formed was adjacent to the red image. The laminate was exposed to
UV rays by means of the device as used above through a cut-off
filter for wavelengths below 400 nm, and then developed in the same
manner as described above. The thus formed green image was embedded
into the adhesive layer using rollers as described above to obtain
a green image in the adhesive layer adjacent to the red image. The
green image had excellent adhesion to the support, and no missing
parts or defects in shape were detected therein.
Furthermore, similar procedures as described above were repeated
for the formation of a blue image, to thereby obtained a glass
plate having a trichromatic image embedded in the adhesive layer
thereof.
Furthermore, a light-shielding black image was formed in the same
manner as described above, except that the exposure was carried out
through a photomask with a striped pattern.
Thus, a glass plate having thereon a matrix-form pattern of red,
green and blue images and a striped black image pattern (for
shielding light) was obtained. No defects in shape were observed in
any of the colored images, and no pin-holes were detected
therein.
Finally, the glass plate was exposed to UV rays on both sides
thereof without interposing a cut-off filter therebetween to cure
the adhesive layer.
In the above-described manner, a glass plate fitted with the color
filter consisting of R-, G- and B-matrix images and a black striped
pattern was obtained.
EXAMPLE 2
(An example utilizing positively working light-sensitive
layers)
Four kinds of positively working, colored, light-sensitive resin
sheets were prepared in the same manner as in Example 1, except
that light-sensitive solutions of four different colors, having the
respective compositions shown in Table 2 below, were coated in the
place of the corresponding coating solutions of Example 1 to give a
dry thickness of 0.5 .mu.m.
In the same manner as Example 1, the transfer, the image-wise
exposure and the development operations were performed repeatedly
to obtain an image-receiving sheet having an image in four
different colors, except that the imagewise exposure was carried
out through a positive-positive type matrix-form mask. Thus, a
glass plate fitted with a color filter composed of R-, G- and
B-matrix images and black stripes, which had been transferred in
their individually intended patterns, was obtained.
TABLE 2 ______________________________________ (Coating
Compositions for Positively Working, light-sensitive, Colored
Layers) R B G Bl (g) (g) (g) (g)
______________________________________ Product of addition reaction
1.02 0.61 0.87 0.61 between acetone/pyrogallol condensate (average
polymeri- zation degree = 3) and 2- diazo-1-naphthol-4-sulfonyl-
chloride Novolak type phenol-formalde- 2.87 1.72 2.44 1.72 hyde
resin (PR-50716, products of Sumitomo Durez Co., Ltd.) Abietic acid
1.23 1.73 1.05 1.73 Irgadine Red BPT 0.15 Sudan Blue 0.15 Lead
phthalocyanine 0.15 Carbon black 0.15 Tricresyl phosphate 0.51 0.31
0.44 0.31 Fluorine-containing surface 0.04 0.04 0.04 0.04 active
agent (FC-430, pro- duct of 3M Co.) Methyl ethyl keto ne 19.0 19.5
17.0 19.0 Ethylene glycol monomethyl 44 44 44 44 ether acetate
Ethylene glycol monomethyl 44 44 44 44 ether
______________________________________
EXAMPLE 3
A polarizing plate fitted with a color filter was obtained in the
same manner as in Example 1, except that a polarizing plate,
Barilite (produced by Sunritsu Denki K.K.), was used in the place
of the glass plate having a thickness of about 1.6 mm.
EXAMPLE 4
A color filter was obtained in the same manner as in Example 1,
except that a polyethylene terephthalate film provided with a
gelatin subbing layer of about 170 .mu.m in thickness was used in
the place of the glass plate having a thickness of about 1.6
mm.
EXAMPLE 5
A color filter was obtained in the same manner as in Example 1,
except that a transparent glass substrate provided with a clear
electrode on one side was used in the place of the glass plate, and
the images were transferred to the electrode side of the
substrate.
In the color filters obtained in Examples 1 to 5, accurate patterns
were formed, and excellent registering of the differently colored
patterns was also effected. Moreover, no spectral changes were
observed in each colored pattern even when these color filters were
stored for 2 hours at 170.degree. C. in contact with air.
EXAMPLE 6
(An example of utilizing a light-insensitive adhesive layer)
A coating composition. described below was coated on a glass plate
having a thickness of 1.6 mm, and dried to form a
light-insensitive, heat-sensitive adhesive layer of 20 .mu.m in dry
thickness. On this adhesive layer, a 30 .mu.m-thick polyethylene
film was laminated as a protective film.
______________________________________ Coating Composition for
Adhesive Layer: ______________________________________ Polyvinyl
butyral (Denka Butyral #2000-L, 4 product of Denki Kagaku Kogyo
Kabushiki Kaisha) Fluorine-containing surface active agent 0.05 g
(Fluorad FC-430, product of 3M Co.) Silane coupling agent KBM-403
(.gamma.-glycidoxy- 2.5 g propyltrimethoxysilane, product of
Shinetsu Silicone Co., Ltd.) Methanol 50 ml Methyl ethyl ketone 20
ml Ethylene glycol monomethyl ether acetate 20 ml
______________________________________
A glass plate fitted with a color filter constructed by matrix-form
images of R, G and B colors and black stripes which had been
transferred thereto in predetermined patterns was obtained in the
same manner as in Example 1, except that the irradiation of the
adhesive layer with UV rays was not conducted.
EXAMPLE 7
(An example of utilizing light-sensitive layers provided with
a subbing layer and a monolayer-form light-sensitive
image-re-receiving layer)
A 5% water solution of PVA (saponification degree=82%,
polymerization degree=about 500) was coated on a polyethylene
terephthalate film (thickness=20 .mu.m) as a temporary support, and
dried for 2 min. at 80.degree. C. to form a subbing layer thereon
of 0.1 .mu.m in dry thickness.
As coating compositions for forming light-sensitive colored resin
layers, light-sensitive solutions of four different colors, a black
color (for a light-shielding layer), a red color (for a R layer), a
green color (for a G layer) and a blue color (for a B layer), were
prepared having the compositions indicated in the following Table 3
below.
TABLE 3 ______________________________________ (Coating
Compositions for Colored, Light-Sensitive Layers) R B G Bl (g) (g)
(g) (g) ______________________________________
Benzylmethacrylate/Methacrylic 62 62 62 62 Acid Copolymer (molar
ratio = 70/30, weight average molecu- lar weight = 20,000)
Pentaerythritol Tetraacrylate 38 38 38 38
2-Benzoylmethylene-3-methyl-.beta.- 3 3 3 3 naphtothiazoline
2-(p-Methoxyphenyl)-4,6-bis- 3 3 3 3 (trichloromethyl)-s-triazine
Carmine 6B (C. I. 12490, red) 20 Phthalocyanine Blue (C. I. 74160,
18 blue) Phthalocyanine Green (C. I. 74260, 18 green) Carbon Black
(MA-100, products 20 of Mitsubishi Chemical Industries, Ltd.)
Cellosolve Acetate 650 650 650 650
______________________________________
The above light-sensitive solutions of four colors were each coated
on four separate temporary supports provided with the
above-described subbing layer, and dried to form light-sensitive
colored resin layers having a dry thickness of 0.5 .mu.m,
respectively.
A 30 .mu.m-thick polyethylene film was laminated as a protective
sheet on each of the light-sensitive colored resin layers.
Thus, four kinds of light-sensitive colored resin sheets
(negatively working, light-sensitive, colored sheets) were
prepared, each consisting of the temporary support, the subbing
layer, the light-sensitive colored resin layer and the protective
sheet, arranged in that order.
Separately, an adhesive layer was formed on a glass plate in the
same manner as in Example 1.
The protective sheet was peeled apart from the light-sensitive red
resin sheet, and the resulting red resin sheet was superposed on
the adhesive layer such that the light-sensitive resin layer was
contacted with the adhesive layer. Then, the superposed material
was subjected to a laminating operation using a laminator (Fast
Laminator 8B-550-80, made by Taisei Shoji K.K.) under a pressure
was 2 Kg/m.sup.2, a roller temperature of 105.degree. C., and a
laminating speed of 0.9 m/min. Thereafter, the temporary support
was peeled apart from the light-sensitive red resin sheet, whereby
the light-sensitive red resin layer was transferred together with
the subbing layer to the glass plate via the adhesive layer.
Subsequently, a mask having a matrix-form pattern was superposed
upon the glass plate, and exposed by means of a ultra-high pressure
mercury lamp of 2 Kw placed at a distance of 50 cm on the mask
side. The thus exposed light-sensitive red resin sheet was
developed for 20 seconds at 35.degree. C. using a developer having
the composition described below, and subsequently washed with water
and dried to obtain a red image on the glass plate.
______________________________________ Composition of Developer:
______________________________________ Sodium carbonate 15 g Butyl
cellosolve 1 g Water 1 g ______________________________________
The red image on the adhesive layer was passed between a pair of
Teflon rollers under a roller surface temperature of 105.degree.
C., a between-roller pressure of 2.0 Kg/cm.sup.2 and a passing
speed of 0.5 m/min. Thus, the red image was embedded into the
adhesive layer.
To the resulting adhesive layer was transferred the light-sensitive
resin layer of a blue color in the same manner as described above.
Then, a matrix-form photomask was superposed on the light-sensitive
blue resin layer such that the blue image to be formed would be
adjacent to the red image. The laminate was exposed, and then
developed in the same manner as described above. In this manner, a
blue image adjacent to the red image was obtained on the adhesive
layer. No defects or missing parts were detected in the thus formed
blue image elements.
Furthermore, similar procedures as described above were repeated
for the formation of a green image, to obtain a glass plate having
a trichromatic image embedded in the adhesive layer thereof.
Furthermore, a black image of a striped pattern was formed in the
same manner as described above, except that the exposure was
carried out through a photomask with a striped pattern.
Thus, a glass plate carrying a black striped image with red, blue
and green matrix patterns was obtained. No missing parts or defects
were observed in any image element, and no pin-holes or turbidity
were detected therein.
EXAMPLE 8
Light-sensitive resin layers provided with a subbing layer on
temporary supports were prepared in the same manner as in Example
7, and a light-sensitive adhesive layer on a glass plate was
prepared in the following manner.
The same coating composition for an adhesive layer as used in
Example 1 was coated-on a temporary support of a polyethylene
terephthalate film (thickness=20 .mu.m), and dried for 2 min. at
100.degree. C. to form a light-sensitive adhesive layer having a
dry thickness of 5 .mu.m. On this light-sensitive adhesive layer, a
20 .mu.m-thick polyethylene film was laminated as a protective
sheet. Thus, a light-sensitive adhesive sheet comprising a
temporary support, a light-sensitive adhesive layer and a
protective sheet, arranged in that order, was obtained.
The protective sheet was peeled apart from the light-sensitive
adhesive sheet, and the resulting adhesive sheet was superposed on
a glass plate (1.6 mm in thickness) previously washed successively
with alkali and water, and then dried with the face of the adhesive
layer turned to the glass surface, followed by a laminating
operation using a laminator (Fast Laminator 8B-550-80, made by
Taisei Shoji K.K.) under a pressure of 2 Kg/cm.sup.2, a roller
temperature of 105.degree. C. and a laminating speed of 0.9 m/min.
Thereafter, the temporary support of the light-sensitive adhesive
sheet was peeled apart, whereby direct transfer of the
light-sensitive adhesive layer to the glass plate was
completed.
In the same manner as in Example 1, light-sensitive resin sheets of
red, green and blue colors were each transferred to the
light-sensitive adhesive layer, and subjected successively to
exposure, development and embedding processes resulting in the
production of a glass provided with a color filter having red,
green and blue matrix images and black stripes formed in a
predetermined pattern.
EXAMPLE 9
(An example of utilizing a monolayer-form adhesive layer of
low sensitivity
A 1.6 mm-thick glass plate was coated with the following coating
composition for forming an adhesive layer, and then dried. Thus, an
adhesive layer having a dry thickness of 5 .mu.m was formed. On
this adhesive layer, a 30 .mu.m-thick polyethylene film was
laminated as a protective film at room temperature.
______________________________________ Coating Composition for
Adhesive Layer: ______________________________________ Methyl ethyl
ketone 2,600 g Dianal BR-77 (acrylic resin, product 168 g of
Mitsubishi Rayon Company Limited) Dianal BR-64 (acrylic resin,
product 168 g of Mitsubishi Rayon Company Limited) Oxylac SH-101
(styrenemonopropyl- 59 g maleate copolymer, product of Nippon
Shokubai Kagaku Kogyo Co., Ltd.) NK Ester TMMT (pentaerythritol
tetra- 216 g acrylate, product of Shin Nakamura Kagaku K.K.)
Megafac F-177P (fluorine-containing 3.8 g surface active agent,
product of Dai-Nippon Ink & Chemicals, Inc.) Hydroquinone
monomethyl ether 0.5 g Irgacure 651 (dimethoxyphenylacetophenone, 3
g product of Ciba Geigy Ltd.) Silane coupling agent KBM-403
(.gamma.-glycidoxy- 2.5 g propyltrimethoxysilane, product of
Shinetsu Silicone Co., Ltd.)
______________________________________
This adhesive layer was lower in sensitivity to UV rays than that
prepared in Example 1 such that UV rays were used for exposure
without a cut-off filter for wavelengths shorter than 400 nm. In
the imagewise exposure of the light-sensitive colored resin layers
carried out after transfer to the adhesive layer, no problems were
encountered in the embedding processing of the colored images, and
no missing image parts or defects in shape of the image elements
were observed.
EXAMPLE 10
(An example of carrying out an embedding operation once
alone)
A polychromatic colored image was formed using the same materials
as in Example 1 but in the following manner.
The protective film was peeled apart from the light-sensitive red
resin sheet, and the resulting sheet was superposed on the glass
plate from which the protective film had been removed, such that
the light-sensitive resin layer was contacted with the adhesive
layer on the glass plate. Then, the superposed material was
subjected to a laminating operation using a laminator (Fast
Laminator 8B-550-80, made by Taisei Shoji K.K.) under a pressure of
2 Kg/m.sup.2, a roller temperature of 105.degree. C., and a
laminating speed of 0.9 m/min. Thereafter, the temporary support
was peeled apart from the light-sensitive red resin sheet, whereby
the light-sensitive red resin layer was transferred to the glass
plate via the adhesive layer.
Subsequently, a photomask having a matrix-form pattern the elements
of which having a one-side length of 120 .mu.m was superposed upon
the light-sensitive red resin layer laminated on the adhesive
layer, and exposed by means of a ultra-high pressure mercury lamp
of 2 Kw through a cut-off filter for wavelengths below 400 nm and
placed at a distance of 50 cm on the photomask side. The thus
exposed light-sensitive red resin layer was developed for 20
seconds at 35.degree. C. using a developer having the composition
described below, and subsequently washed with water and dried to
obtain a red image on the glass plate.
______________________________________ Composition of Developer:
______________________________________ Sodium carbonate 15 g Butyl
cellosolve 1 g Water 1 g ______________________________________
To the resulting adhesive layer was transferred the light-sensitive
resin layer of a green color in the same manner as described above.
Then, a matrix-form photomask was superposed on the light-sensitive
green resin layer such that the green image to be formed would be
adjacent to the red image, exposed to UV rays through a cut-off
filter for wave-lengths below 400 nm, and then developed in the
same manner as described above. A green-image adjacent to the red
image was thus obtained on the adhesive layer. The green image had
excellent adhesion to the support, and no missing parts or defects
in shape were detected therein.
Furthermore, similar procedures as described above were repeated
for the formation of a blue image, to obtain a glass plate
containing a trichromatic image embedded in the adhesive layer
thereof.
Furthermore, a light-shielding black image was formed in the same
manner as described above, except that the exposure was carried out
through a photomask with a striped pattern.
Thus, a glass plate carrying matrix-form pattern of red, green and
blue images on which a light-shielding (black striped) pattern was
superimposed was obtained. No defects in shape were observed in any
of the colored images, and no pin-holes were detected therein.
A 20 .mu.m-thick polyethylene terephthalate film, the surface of
which had been treated with a silicone lubricant, was inserted
between one of a pair of rollers and the multi-color image on the
adhesive layer with its lubricant-treated face turned to the face
of the multicolor image. The multicolor image covered with the film
was passed between the pair of rollers under a controlled roller
surface temperature of 105.degree. C., a between-roller pressure of
2.0 Kg/cm.sup.2 and a passing speed of 0.5 m/min, to thereby embed
the multicolor image in the adhesive layer. No defects in shape
were observed in any of image elements, and no pin-holes were
detected therein.
Finally, the glass plate was exposed to UV rays on both sides
thereof without interposing a cut-off filter therebetween.
In the above-described manner, a glass plate provided with a color
filter consisting of R-, G- and B-matrix images and a black striped
pattern was obtained.
COMPARATIVE EXAMPLE 1
After the red image was formed on the adhesive layer in the same
manner as in Example 1, the light-sensitive resin layer of a green
color was laminated on the resulting adhesive layer without
embedding the resin layer using rollers. The green resin layer was
not in close contact with the image-receiving layer, such that the
green image formed by subsequent exposure and development
processings resulted in an unacceptable level of missing parts, and
bubbles were observed between the green image and the
image-receiving layer.
As described in detail above, a polychromatic colored image of
excellent quality is obtained in accordance with the methods of the
present invention.
The effects of the present invention are achieved when an image
forming material having a peel-apart layer is used, and the
temporary support thereof is peeled apart before imagewise
exposure.
While the invention has been described in detail and with reference
to specific examples thereof, it will be apparent to one skilled in
the art that various changes and modifications can be made therein
without departing from the spirit and scope thereof.
* * * * *